CN105749922B - A kind of heavy oil hydrogenating treatment catalyst preparation method and thus obtained catalyst and its application - Google Patents
A kind of heavy oil hydrogenating treatment catalyst preparation method and thus obtained catalyst and its application Download PDFInfo
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Abstract
The present invention provides a kind of heavy oil hydrogenating treatment catalyst preparation method and thus obtained catalyst and its application, the heavy oil hydrogenating treatment catalyst preparation method include：Shaped alumina alumina supporter is subjected to hydro-thermal process in confined conditions, obtains hydro-thermal process aluminium oxide；Then at least one metal component selected from group vib and at least one metal component selected from VIII group are loaded on the hydro-thermal process aluminium oxide, obtains heavy oil hydrogenating treatment catalyst；Wherein, it is counted by oxide and on the basis of unit carrier surface load capacity, the content of group vib metal component is 4.8 μm of ol/m in the catalyst2‑9.0μmol/m2, the content of group VIII metal component is 1.5 μm of ol/m in the catalyst2‑4.0μmol/m2.Compared with the preparation method of existing heavy oil hydrogenating treatment catalyst, the catalyst prepared by the preparation method of heavy oil hydrogenating treatment catalyst using the present invention carries out having better hydrodesulfurization, denitrogenation and de- carbon residue effect when heavy-oil hydrogenation processing.
Description
Technical field
The present invention relates to a kind of preparation method of heavy oil hydrogenating treatment catalyst, catalyst obtained by this method and make
With the heavy oil hydrogenation treatment method of the catalyst.
Background technology
Processing of heavy oil, particularly to residual oil carry out deep processing, not only contribute to improve crude oil utilization rate, alleviate the energy
The nervous trend of supply, while can also reduce environmental pollution, realize the efficient clean utilization of the energy.
Heavy oil is enriched the impurity such as sulphur, nitrogen, metal, the carbon residue of crude oil, these impurity are to subsequent process and production
Moral character matter has serious adverse effect, thus must be removed.Since the impurity such as sulfur in heavy oil, nitrogen are mostly enriched in big point
Among the multiring aromatic hydrocarbon species of son, it is more difficult to remove, therefore it is required that carrying out the catalysis of the correlated responses such as desulfurization, denitrogenation and de- carbon residue
Agent has higher catalytic activity.Catalyst reaction activity is directly related with calculation in catalyst surface active, surface have compared with
More activated centres is beneficial to the active promotion of catalyst reaction.The increase at catalyst surface active center can not pass through raising
(i.e. the load capacity of metal component) and simple realization are measured on the active metal of catalyst, because increasing in conventional catalyst preparation method
Add amount on metal that can lead to accumulation of metal, reduces the utilization rate of active metal instead.Therefore improve the dispersity of active metal,
The aggregation for avoiding active metal improves the utilization rate of active metal, is the pass developed high-performance heavy oil desulfurization, take off carbon residue catalyst
Key.
Patent ZL201110187353.3 discloses a kind of Hydrobon catalyst, which is to be supported on titanium to be modified oxygen
Change molybdenum, cobalt, three component catalyst of nickel on alumina supporter, wherein by weight, oxidation molybdenum content is 4~18%, nickel oxide content
It is 0.2~5%, cobalt oxide content is 2.0~7.5%.Specific preparation method is to be impregnated by the total immersion solution containing molybdenum, nickel and cobalt
Dry and calcination for activation is made after carrier.
Nickel molybdenum or cobaltmolybdate catalyst disclosed in the prior art, are not easy have higher activity due to the aggregation between metal
Tenor, the especially content of active oxidation molybdenum can not improve, which results in the activated centre quantity of catalyst surface is limited,
Affect the active raising of catalyst reaction.
Invention content
The technical problem to be solved by the present invention is to, for the prior art provide heavy oil hydrogenating treatment catalyst with compared with
The aggregation that active metal can not be avoided when high metal content provides the drawbacks of reduction so as to cause catalyst surface active center
It is a kind of new with more preferable desulfurization, denitrification effect and the excellent heavy oil hydrogenating treatment catalyst and its preparation of carbon residue conversion performance
Method and application.
To achieve the goals above, the present invention provides a kind of heavy oil hydrogenating treatment catalyst preparation method, and this method includes：
Shaped alumina alumina supporter is subjected to hydro-thermal process in confined conditions, obtains hydro-thermal process aluminium oxide；It then will be selected from group vib
At least one metal component and at least one metal component selected from VIII group load on the hydro-thermal process aluminium oxide, obtain
Heavy oil hydrogenating treatment catalyst；Wherein, it is counted by oxide and on the basis of unit carrier surface load capacity, in the catalyst
The content of group vib metal component is 4.8 μm of ol/m2-9.0μmol/m2, the content of group VIII metal component is in the catalyst
1.5μmol/m2-4.0μmol/m2。
Preferably, wherein counted by oxide and on the basis of unit carrier surface load capacity, described in the catalyst
The content of group vib metal component is 5.4 μm of ol/m2-8.0μmol/m2, group VIII metal component contains described in the catalyst
Amount is 1.8 μm of ol/m2-3.6μmol/m2。
Preferably, wherein counted by oxide and on the basis of unit carrier surface load capacity, described in the catalyst
The content of group vib metal component is 5.9 μm of ol/m2-7.5μmol/m2, group VIII metal component contains described in the catalyst
Amount is 2.0 μm of ol/m2-3.1μmol/m2。
Preferably, wherein the shaped alumina alumina supporter include in γ-, η-, θ-, δ-and χ-alumina crystalline phase at least
A kind of crystalline phase.
Preferably, wherein the shaped alumina alumina supporter is with containing in boron, fluorine, silicon, titanium, alkaline earth and alkali metal
The compound of at least one modifying element be modified processed modified aluminium oxide supports.
Preferably, wherein the preparation process of the modified aluminium oxide supports includes：It introduces and contains into the predecessor of aluminium oxide
There is the compound selected from least one of boron, fluorine, silicon, titanium, alkaline earth and alkali metal modifying element, then will introduce described change
The aluminum oxide precursor object of property element is molded, and aluminum oxide precursor object after molding is roasted.
Preferably, wherein the shaped alumina alumina supporter be selected from spherical shape, cylinder, annular, cloverleaf pattern, quatrefoil,
At least one of honeycombed and butterfly shape.
Preferably, wherein the temperature of the hydro-thermal process is 60-180 DEG C, and the time is 1-24 hours, by weight, described
The dosage of water is the 100-300 weights % of the formed alumina vehicle weight in hydro-thermal process.
Preferably, wherein the temperature of the hydro-thermal process is 90-150 DEG C, and the time is 4-12 hours, by weight, described
The dosage of water is the 150-250 weights % of the formed alumina vehicle weight in hydro-thermal process.
Preferably, wherein this method further includes that the hydro-thermal process aluminium oxide before load is dried, the load
The drying temperature of preceding hydro-thermal process aluminium oxide is 60-350 DEG C, and drying time is 1-48 hours.
Preferably, wherein the group vib metal component be molybdenum and/or tungsten, the group VIII metal group be divided into nickel and/or
Cobalt.
Preferably, wherein the group vib metal component is molybdenum, and the group VIII metal group is divided into nickel and/or cobalt.
Preferably, wherein loaded to the group vib metal component and the group VIII metal component by dipping described
On hydro-thermal process aluminium oxide.
Preferably, wherein this method further includes：Hydro-thermal process aluminium oxide after dipping is dried, is then roasted
It burns or does not roast；The temperature of the drying is 60-150 DEG C, and the dry time is 1-5 hours；The temperature of the roasting is 350-550
DEG C, the time of roasting is 1-6 hours.
The present invention also provides a kind of heavy oil hydrogenating treatment catalyst, which is according to the present invention's
It is prepared by the preparation method of heavy oil hydrogenating treatment catalyst.
The present invention further provides a kind of heavy oil hydrogenation treatment method, this method includes：Under heavy-oil hydrogenation treatment conditions,
The heavy oil hydrogenating treatment catalyst prepared by preparation method by heavy oil with heavy oil hydrogenating treatment catalyst according to the present invention connects
It touches and carries out heavy-oil hydrogenation processing.
Preferably, in the heavy oil hydrogenation treatment method, the heavy oil is selected from crude oil, reduced crude, decompression residuum, depth
Pull out at least one of wax oil, frivolous coal tar and wax tailings.
Preferably, in the heavy oil hydrogenation treatment method, the heavy-oil hydrogenation treatment conditions include：Reaction temperature 300-
550 DEG C, hydrogen partial pressure 4-20 megapascal, liquid hourly space velocity (LHSV) 0.1-3 hours-1, hydrogen to oil volume ratio 200-2500.
Compared with the preparation method of existing heavy oil hydrogenating treatment catalyst, heavy oil hydrogenating treatment catalyst using the present invention
Preparation method prepared by catalyst carry out heavy-oil hydrogenation processing when have better hydrodesulfurization, denitrogenation and de- carbon residue effect
Fruit.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is catalyst C1 (the i.e. embodiments 5 prepared by the preparation method by the heavy oil hydrogenating treatment catalyst of the present invention
Prepared catalyst) XRD spectra；
Fig. 2 is catalyst DC1 (i.e. comparative examples 1 prepared by the preparation method of the heavy oil hydrogenating treatment catalyst of the prior art
Prepared catalyst) XRD spectra.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched
The specific implementation mode stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of heavy oil hydrogenating treatment catalyst preparation method, and this method includes：By shaped alumina alumina supporter
Hydro-thermal process is carried out in confined conditions, obtains hydro-thermal process aluminium oxide；Then by least one metal component selected from group vib
It is loaded on the hydro-thermal process aluminium oxide at least one metal component selected from VIII group, obtains heavy-oil hydrogenation processing catalysis
Agent；Wherein, it is counted by oxide and on the basis of unit carrier surface load capacity, group vib metal component contains in the catalyst
Amount is 4.8 μm of ol/m2-9.0μmol/m2, preferably 5.4 μm of ol/m2-8.0μmol/m2, further preferably 5.9 μm of ol/m2-
7.5μmol/m2；The content of group VIII metal component is 1.5 μm of ol/m in the catalyst2-4.0μmol/m2, preferably 1.8 μ
mol/m2-3.6μmol/m2, further preferably 2.0 μm of ol/m2-3.1μmol/m2.Wherein, the unit carrier surface load
Amount refers to the load capacity on unit carrier surface area, i.e., the ratio between the load capacity of metal component and carrier total surface area in catalyst,
Carrier described herein refers to the shaped alumina alumina supporter before hydro-thermal process.The size of the carrier total surface area according to
RIPP151-90 standard methods are measured using BET method.
Heavy oil hydrogenating treatment catalyst preparation method according to the present invention, the shaped alumina alumina supporter may include ability
The aluminium oxide of various crystalline phases known to field technique personnel, for example, may include the alumina crystalline phases such as γ-, η-, θ-, δ-and χ-
At least one of crystalline phase.It, can be by the way that predecessor of aluminium oxide, such as boehmite etc. be molded so in the present invention
After roast and obtain the shaped alumina alumina supporter, can also directly buy the aluminium oxide including above-mentioned alumina crystalline phase carry out at
Shaped alumina alumina supporter is obtained after type.
Heavy oil hydrogenating treatment catalyst preparation method according to the present invention, the shaped alumina alumina supporter can be with containing
Compound selected from least one of boron, fluorine, silicon, titanium, alkaline earth and alkali metal modifying element is modified processed modification
Alumina support.The method of the modification is well-known to those skilled in the art, for example, the modified aluminium oxide supports
Preparation process may include：To the predecessor of aluminium oxide, for example, in boehmite introduce containing selected from boron, fluorine, silicon, titanium,
Then the compound of at least one of alkaline earth and alkali metal modifying element will introduce the aluminum oxide precursor of the modifying element
Object is molded, and aluminum oxide precursor object after molding is roasted.The compound containing modifying element can be selected from
At least one of oxide, acid, alkali and salt arbitrarily containing the modifying element.By institute in the modification of the present invention
It is less to introduce the compound containing modifying element, therefore the shaped alumina alumina supporter Jing Guo modification generally also maintains pure oxygen
Change the crystalline phase of aluminium.
Heavy oil hydrogenating treatment catalyst preparation method according to the present invention, can according to the specifically used requirement of catalyst,
Aluminium oxide or its predecessor are molded using shaping jigs such as banded extruders, this is institute in hydrotreating catalyst preparation process
Commonly, such as：The shaped alumina alumina supporter can be selected from spherical shape, cylinder, annular, cloverleaf pattern, quatrefoil, honeycomb
At least one of shape and butterfly etc. shape.
Heavy oil hydrogenating treatment catalyst preparation method according to the present invention, the hydro-thermal process and conventional catalyst high temperature
Unlike steam treatment, the hydro-thermal process of shaped alumina alumina supporter refers to putting shaped alumina alumina supporter and water in the present invention
Enter in the closed containers such as reaction kettle, be heated to certain temperature in confined conditions, then carries out water at a temperature of the hydro-thermal process
Heat treatment.Shaped alumina alumina supporter after hydro-thermal process can make the metal component of load that better dispersity be presented, and improve
The number of active center and catalytic activity of prepared catalyst.Wherein, the hydro-thermal process temperature can be 60-180 DEG C, preferably
It is 90-150 DEG C；The time of the hydro-thermal process can be 1-24 hours, preferably 4-12 hours；By weight, the hydro-thermal
The dosage of water can be the 100-300 weight % of the formed alumina vehicle weight, the preferably described formed alumina in processing
The 150-250 weights % of vehicle weight.In the present invention, the pressure of hydro-thermal process is self-generated pressure under confined conditions, when the water
When heat treatment carries out at a constant temperature, hydro-thermal process temperature is the thermostat temperature, and the time of the hydro-thermal process is from described closed
Container starts timing when reaching the hydro-thermal process temperature；The heating rate of temperature-rise period before hydro-thermal process is not special
Limitation, preferably 5-15 DEG C/min, more preferably 8-12 DEG C/min.
Heavy oil hydrogenating treatment catalyst preparation method according to the present invention, can also be before load by the hydro-thermal process oxygen
Change aluminium to be dried, to remove the moisture in oxidation aluminium surface and duct.The condition of the drying is not particularly limited, Ke Yiwei
The conventional selection of this field, be subject to can remove oxidation aluminium surface and duct in moisture.Usually, the drying can be
Carry out at a temperature of 60-350 DEG C, preferably carried out at a temperature of 80-200 DEG C, more preferably at a temperature of 100-150 DEG C into
Row.The time of the drying can make appropriate choice according to dry temperature, be not particularly limited.Usually, described dry
The dry time can be 1-48 hours, preferably 1-24 hours, more preferably 1-8 hours.
Heavy oil hydrogenating treatment catalyst preparation method according to the present invention, as living on the heavy oil hydrogenating treatment catalyst
Property center metal component be it is well-known to those skilled in the art, mainly include VIB and group VIII metal component.The VIB
Race's metal component can be molybdenum and/or tungsten, preferably molybdenum；The group VIII metal component can be nickel and/or cobalt.
Heavy oil hydrogenating treatment catalyst preparation method according to the present invention, on alumina the method for carried metal component be
It is well-known to those skilled in the art, for example, can be by impregnating the group vib metal component and the group VIII metal group
Divide and load on the hydro-thermal process aluminium oxide, that is, use the compound containing the group vib metal component and contains the VIII group
The solution of the compound of metal component impregnates hydro-thermal process aluminium oxide.The compound of the metal component containing group vib can be contained
The compound of molybdenum and/or tungstenic metal component can be selected from one or more of its soluble compound, such as selected from oxidation
One or more of molybdenum, tungsten oxide, molybdate, tungstates, metatungstate and paramolybdate, preferably be selected from molybdenum oxide therein,
One or more of ammonium molybdate, ammonium paramolybdate and metatungstate；The compound of more preferable self-contained molybdenum component, such as selected from
One or more of molybdenum oxide, molybdate and paramolybdate.The compound of the component containing group VIII metal can be nickeliferous
And/or the compound of the metal component containing cobalt, it can be selected from their one or more of soluble compound, be such as selected from nitric acid
Cobalt, cobalt acetate, basic cobaltous carbonate, cobalt chloride, the soluble complexes of cobalt, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride
One or more of with the soluble complexes of nickel, it preferably is selected from cobalt nitrate, basic cobaltous carbonate, nickel nitrate and basic nickel carbonate
One or more.The dipping is well-known to those skilled in the art, can be equivalent impregnation, can also be excessive leaching
It can also be step impregnation that stain, which can be co-impregnation, such as the solution containing individual various metal component compounds may be used
It is soaked respectively accumulated water heat treated aluminum, the mixed solution of the component composition containing various metals can also be used to impregnate hydro-thermal process oxygen
Change aluminium.By adjusting the concentration of the dipping solution of metallic components compound described in dipping process and the dosage of dipping solution,
Those skilled in the art can control the content for the metal component being introduced into catalyst, and which is not described herein again.
Heavy oil hydrogenating treatment catalyst preparation method according to the present invention, can also be by the hydro-thermal process aluminium oxide after dipping
It is dried, then carries out roasting or not roasting.The method and condition of the drying and roasting is that those skilled in the art institute is ripe
Know, for example, dry temperature can be 60-150 DEG C, preferably 80-120 DEG C；The dry time can be 1-5 hours, preferably
It is 2-4 hours；The temperature of roasting can be 350-550 DEG C, preferably 400-500 DEG C；The time of roasting can be 1-6 hours,
Preferably 2-4 hours.
The present invention also provides a kind of heavy oil hydrogenating treatment catalyst, which is according to the present invention's
It is prepared by heavy oil hydrogenating treatment catalyst preparation method.
With the catalyst for preparing high metal component load capacity using the preparation method of existing heavy oil hydrogenating treatment catalyst
Unlike, the catalyst of the high metal component load capacity prepared by method using the present invention, metal component is in catalyst table
Well dispersed, not a large amount of aggregations, for example, heavy oil hydrogenating treatment catalyst preparation method using the present invention preparation is urged in face
Agent, and the group vib metal component loaded is molybdenum (Mo), when prepared catalyst is carried out XRD characterization, in the angle of diffraction
2 θ=26 ° ± 2 ° do not have MoO3Characteristic peak occur, this explanation with MoO3Existing metal component Mo carrier surface disperse compared with
Good, not a large amount of aggregations are not enough to be detected MoO3Characteristic peak.And present inventor has further discovered that being made in this way
Metal component the well dispersed catalyst of catalyst surface have higher reactivity.
Heavy oil hydrogenating treatment catalyst provided by the invention can be used alone, and can also make with other catalyst combinations
With hydrotreating of the catalyst particularly suitable for heavy oil especially poor residuum, to be subsequent technique (such as catalytic cracking
Technique) qualified feedstock oil is provided.
The present invention further provides a kind of heavy oil hydrogenation treatment method, this method includes：Under heavy-oil hydrogenation treatment conditions,
Heavy oil is contacted simultaneously with heavy oil hydrogenating treatment catalyst prepared by heavy oil hydrogenating treatment catalyst preparation method according to the present invention
Carry out heavy-oil hydrogenation processing.
In the present invention, the heavy oil can be the various heavy oil feedstocks for needing to carry out hydrotreating, preferably various needs
Carry out the heavier hydrocarbon feeds of hydrodesulfurization, denitrogenation and the processing of de- carbon residue.Specifically, the heavy oil can be selected from crude oil, often
Press at least one of residual oil, decompression residuum, deep drawing wax oil, frivolous coal tar and wax tailings.At the heavy-oil hydrogenation of the present invention
Reason method is to carry out hydrotreating to heavy oil with higher efficiency by contacting heavy oil with catalyst provided by the invention, right
It is not particularly limited in remaining condition of hydrotreating, can be according to the property of pending heavy oil, the routine according to this field
Knowledge makes appropriate choice.For example, the heavy-oil hydrogenation treatment conditions can be：300-550 DEG C of reaction temperature, hydrogen partial pressure 4-
20 megapascal, liquid hourly space velocity (LHSV) 0.1-3 hours-1, hydrogen to oil volume ratio 200-2500；The heavy-oil hydrogenation treatment conditions are preferably：Reaction
350-450 DEG C of temperature, hydrogen partial pressure 8-16 megapascal, liquid hourly space velocity (LHSV) 0.15-2 hours-1, hydrogen to oil volume ratio 400-2000.
Heavy-oil hydrogenation processing can it is any be enough to make the heavy oil under heavy-oil hydrogenation treatment conditions with it is described heavy
Oil hydrogenating treatment catalyst is contacted and carried out in the reactor of hydrotreating, for example, can be in fixed bed reactors, movement
It is carried out in bed reactor or fluidized bed reactor.
Heavy oil hydrogenation treatment method according to the present invention, the catalyst before the use, can be in the routines of this field
Under the conditions of first carry out presulfurization.The condition of presulfurization can be：In presence of hydrogen, with sulphur, sulphur at a temperature of 140-370 DEG C
Change hydrogen or presulfurization is carried out to catalyst containing sulfur feedstock, the presulfurization can carry out outside the reactor also can be described anti-
It answers In-situ sulphiding in device.
The present invention will be further detailed by embodiment below, but it is not thereby limiting the invention.
Agents useful for same in following embodiment and comparative example is except as expressly described chemically pure reagent.
In following embodiment and comparative example, the radial crushing that carrier is measured using method specified in RIPP 25-90 is strong
Degree；Using method specified in RIPP 151-90 measure the total surface area of carrier, the Kong Rong of carrier and carrier can several Kong Zhi
Diameter；The molybdenum of catalyst, the content of nickel and cobalt are measured using the x ray fluorescence spectrometry (that is, XRF) in RIPP133-90；Using
The boron of Coupled Plasma-Atomic Emission Spectrometric Determination catalyst in RIPP128-90, the content of silicon, fluorine；It is herein and mentioned below
RIPP standard methods for details, reference can be made to《Petrochemical analysis method》, Yang Cui is surely equal to be compiled, nineteen ninety version.
In following embodiment and comparative example, the distribution of active metal component in catalyst is measured by x-ray powder diffraction instrument
State is confirmed whether have molybdenum trioxide to form aggregation, and instrument uses Philips XPERT Series X-ray powder diffractometers, test
Condition is：Cu K alpha rays (λ=0.154nm), Ni filters, voltage 40kV, electric current 30mA, scanning range are 5~70 °.
Embodiment 1-4 provides the preparation method of the shaped alumina alumina supporter of the present invention and prepared formed alumina carries
Body.
Embodiment 1
The boehmite dry glue powder RPB90 of 1 kilogram of Chang Ling catalyst plant production and 30 grams of sesbania powder are uniformly mixed,
The obtained mixture is uniformly mixed with the aqueous solution of nitric acid of 1.1 liters of a concentration of 1 weight % at room temperature, in twin-screw extrusion
Continue kneading on machine after plastic, to be extruded into the cloverleaf pattern item of 1.1 millimeters of ф, wet bar is after 120 DEG C 3 hours dry, in 600
DEG C roasting obtains shaped alumina alumina supporter Z1 in 3 hours.The materialization for measuring Z1 the results are shown in Table 1.
Embodiment 2
The boehmite dry glue powder RPB100 of 1 kilogram of Chang Ling catalyst plant production and 30 grams of sesbania powders are uniformly mixed,
At room temperature by the aqueous solution 1.2 of the obtained mixture and 20g containing diboron trioxide, nitric acid 25 milliliters (mass fraction 65%)
It rises and is uniformly mixed, continue kneading on double screw banded extruder after plastic, to be extruded into the butterfly item of 1.1 millimeters of ф, wet bar is through 110
DEG C after dry 2 hours, shaped alumina alumina supporter Z2 is obtained within 3 hours in 700 DEG C of roastings.The materialization for measuring Z2 the results are shown in Table 1.
Embodiment 3
The boehmite dry glue powder RPB90 of 1 kilogram of Chang Ling catalyst plant production and 30 grams of sesbania powder are uniformly mixed,
At room temperature by the aqueous solution of nitric acid and the % containing the weight of silica 30 of the obtained mixture and 1.1 liters of a concentration of 1 weight %
120 grams of Ludox is uniformly mixed, and continues kneading on double screw banded extruder after plastic, to be extruded into the trilobal of 1.1 millimeters of ф
Item, wet bar obtain shaped alumina alumina supporter Z3 in 3 hours after 120 DEG C 3 hours dry, in 600 DEG C of roastings.Measure the materialization knot of Z3
Fruit is shown in Table 1.
Embodiment 4
The boehmite dry glue powder RPB100 of 1 kilogram of Chang Ling catalyst plant production and 30 grams of sesbania powders are uniformly mixed,
It is at room temperature that 1.2 liters of the aqueous solution of the obtained mixture and 90g containing ammonium fluoride, nitric acid 25 milliliters (mass fraction 65%) is mixed
It closes uniformly, continues kneading on double screw banded extruder after plastic, to be extruded into the butterfly item of 1.1 millimeters of ф, wet bar is dry through 110 DEG C
After dry 2 hours, shaped alumina alumina supporter Z4 is obtained within 3 hours in 700 DEG C of roastings.The materialization for measuring Z4 the results are shown in Table 1.
Embodiment 5-8 provides the specific preparation method of the heavy oil hydrogenating treatment catalyst of the present invention and prepared catalysis
Agent.
Embodiment 5
Weigh Z1 carriers 150g be placed in hydration kettle in, be added 150g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, control heating rate are 10 DEG C of min-1, treatment temperature is 80 DEG C, and the time is 12 hours.After the completion of hydro-thermal
Aluminium oxide is filtered, it is then 8 hours dry at 120 DEG C, obtain the alumina support BZ1 of hydrothermal treatment.
100 grams of carrier BZ1 after water intaking heat treatment contains MoO with 220 milliliters3170 grams per liters, the molybdic acid of 30 grams per liters of NiO
Ammonium, nickel nitrate mixed solution impregnate 1 hour, are dried in 120 DEG C after filtering 2 hours, 410 DEG C roast 4 hours, obtain catalyst
C1.It is counted by oxide and on the basis of unit carrier surface load capacity, is measured in catalyst C1 using Xray fluorescence spectrometer
Whether the content of molybdenum oxide, nickel oxide, being measured in catalyst C1 using x-ray powder diffraction instrument has molybdenum trioxide to form aggregation,
Measurement result is as shown in table 2, and the XRD spectra of catalyst C1 is as shown in Figure 1.
Embodiment 6
Weigh Z2 carriers 150g be placed in hydration kettle in, be added 225g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, control heating rate are 10 DEG C of min-1, treatment temperature is 100 DEG C, and the time is 6 hours.After the completion of hydro-thermal
Aluminium oxide is filtered, it is then 6 hours dry at 90 DEG C, obtain the alumina support BZ2 of hydrothermal treatment.
100 grams of carrier B Z2 after water intaking heat treatment contains MoO with 110 milliliters3260 grams per liters, 18 grams per liters of NiO, CoO
The molybdenum oxides of 42 grams per liters, basic nickel carbonate, basic cobaltous carbonate mixed solution impregnate 0.5 hour, dried 2 hours in 120 DEG C,
450 DEG C roast 2 hours, obtain catalyst C2.It is counted by oxide and on the basis of unit carrier surface load capacity, using X-ray
The content of molybdenum oxide, nickel oxide, cobalt oxide in Fluorescence Spectrometer measurement catalyst C2, is measured using x-ray powder diffraction instrument
Whether there is molybdenum trioxide to form aggregation in catalyst, measurement result is as shown in table 2.
Embodiment 7
Weigh Z3 carriers 150g be placed in hydration kettle in, be added 375g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, control heating rate are 10 DEG C of min-1, treatment temperature is 120 DEG C, and the time is 8 hours.After the completion of hydro-thermal
Aluminium oxide is filtered, it is then 3 hours dry at 160 DEG C, obtain the alumina support BZ3 of hydrothermal treatment.
100 grams of carrier B Z3 after water intaking heat treatment contains MoO with 120 milliliters3290 grams per liters, the oxygen of 63 grams per liters of CoO
Change molybdenum, basic cobaltous carbonate mixed solution impregnate 1 hour, in 120 DEG C dry 2 hours, 480 DEG C roast 4 hours, obtain catalyst
C3.It is counted by oxide and on the basis of unit carrier surface load capacity, is measured in catalyst C3 using Xray fluorescence spectrometer
The content of molybdenum oxide, cobalt oxide, whether have molybdenum trioxide form aggregation, survey if being measured in catalyst using x-ray powder diffraction instrument
It is fixed that the results are shown in Table 2.
Embodiment 8
Weigh Z4 carriers 150g be placed in hydration kettle in, be added 450g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, control heating rate are 10 DEG C of min-1, treatment temperature is 150 DEG C, and the time is 4 hours.After the completion of hydro-thermal
Aluminium oxide is filtered, it is then 3 hours dry at 160 DEG C, obtain the alumina support BZ4 of hydrothermal treatment.
100 grams of carrier B Z4 after water intaking heat treatment contains MoO with 220 milliliters3260 grams per liters, 18 grams per liters of NiO, CoO
Molybdenum oxide, basic nickel carbonate, the basic cobaltous carbonate mixed solution of 41 grams per liters impregnate 1 hour, small in 110 DEG C of drying 3 after filtering
When, 450 DEG C roast 2 hours, obtain catalyst C4.It is counted by oxide and on the basis of unit carrier surface load capacity, is penetrated using X
The content of molybdenum oxide, nickel oxide, cobalt oxide in line Fluorescence Spectrometer measurement catalyst C4, is surveyed using x-ray powder diffraction instrument
Determine whether there is molybdenum trioxide to form aggregation in catalyst, measurement result is as shown in table 2.
Comparative example 1-5 provides the preparation method of heavy oil hydrogenating treatment catalyst in the prior art and prepared catalysis
Agent.
Comparative example 1
Aluminium oxide Z1 using not hydrothermal treatment is carrier, and ginseng is made using the active component carrying method of embodiment 5
Than catalyst DC1.It is counted by oxide and on the basis of unit carrier surface load capacity, is urged using Xray fluorescence spectrometer measurement
The content of molybdenum oxide, nickel oxide in agent DC1 measures in catalyst whether have molybdenum trioxide using x-ray powder diffraction instrument
Aggregation is formed, measurement result is as shown in table 2, and XRD spectra is as shown in Figure 2.
Comparative example 2
Aluminium oxide Z2 using not hydrothermal treatment is carrier, and ginseng is made using the active component carrying method of embodiment 6
Than catalyst DC2.It is counted by oxide and on the basis of unit carrier surface load capacity, is urged using Xray fluorescence spectrometer measurement
The content of molybdenum oxide, nickel oxide, cobalt oxide in agent DC2 measures in catalyst whether have three using x-ray powder diffraction instrument
Molybdenum oxide forms aggregation, and measurement result is as shown in table 2.
Comparative example 3
Aluminium oxide Z3 using not hydrothermal treatment is carrier, and ginseng is made using the active component carrying method of embodiment 7
Than catalyst DC3.It is counted by oxide and on the basis of unit carrier surface load capacity, is urged using Xray fluorescence spectrometer measurement
The content of molybdenum oxide, cobalt oxide in agent DC3 measures in catalyst whether have molybdenum trioxide using x-ray powder diffraction instrument
Aggregation is formed, measurement result is as shown in table 2.
Comparative example 4
Aluminium oxide Z4 using not hydrothermal treatment is carrier, and ginseng is made using the active component carrying method of embodiment 8
Than catalyst DC4.It is counted by oxide and on the basis of unit carrier surface load capacity, is urged using Xray fluorescence spectrometer measurement
The content of molybdenum oxide, nickel oxide, cobalt oxide in agent DC4 measures in catalyst whether have three using x-ray powder diffraction instrument
Molybdenum oxide forms aggregation, and measurement result is as shown in table 2.
Comparative example 5
It weighs Z1 carriers 100g to be placed in tube furnace, the air blast into stove with 100ml/ minutes air quantity, while with 120ml/
Hour rate is pumped into deionized water into stove, and 500 DEG C are warming up to 2 DEG C/min of rates, in 500 DEG C of constant temperature 3 hours, by carrier
Steam treatment is carried out, alumina support DZ1 is obtained.
Aluminium oxide DZ1 using steam treatment is carrier, and reference is made using the active component carrying method of embodiment 5
Catalyst DC5.It is counted by oxide and on the basis of carrier surface load capacity of the unit without steam treatment, it is glimmering using X-ray
The content of molybdenum oxide, nickel oxide in photothermal spectroscopic analyzer measurement catalyst DC5, is measured using x-ray powder diffraction instrument in catalyst
Whether there is molybdenum trioxide to form aggregation, measurement result is as shown in table 2.
Embodiment 9-12
Embodiment 9-12 provides the specific implementation mode of the heavy oil hydrogenation treatment method of the present invention, and illustrates according to the present invention
The hydrotreating performance of catalyst C1, C2, C3, C4 prepared by method.
It is 16ppm with nickel content, content of vanadium 18ppm, sulfur content 3.2%, carbon residue 11%, nitrogen content 0.3%
Reduced crude is raw material, evaluates catalyst on 100 milliliters of small fixed reactors, the results are shown in Table 3.
It is filled into fixed bed reaction after catalyst C1, C2, C3, C4 are broken into the particle of 0.8-1.2 millimeters of diameter respectively
In device, catalyst loading is 100 milliliters.Reaction condition is：380 DEG C of reaction temperature, 14 megapascal of hydrogen partial pressure, liquid hourly space velocity (LHSV) 0.6
Hour-1, hydrogen to oil volume ratio 1000, reaction samples after 200 hours, using inductive coupling plasma emission spectrograph (ICP-
AES) measure treated oil in nickel and vanadium content.(instrument is U.S. PE companies PE-5300 type plasma light quantities
Meter, specific method are shown in petrochemical analysis method RIPP124-90).
The content of sulphur is measured using coulometry (specific method is shown in petrochemical analysis method RIPP62-90).
The content of nitrogen is measured using coulometry (specific method is shown in petrochemical analysis method RIPP63-90).
It uses microdetermination carbon residue content (specific method is shown in petrochemical analysis method RIPP148-90).
The removal efficiency of sulphur, carbon residue, nitrogen and metal is calculated separately according to the following formula：
Comparative example 6-10
Every impurity removal performance of catalyst DC1, DC2, DC3, DC4 and DC5 are evaluated according to the method for embodiment 9-12,
It the results are shown in Table 3.
Catalyst provided by the present invention does not go out nearby at 26 ° ± 2 ° it can be seen from the result of table 2, Fig. 1 and Fig. 2
The characteristic peak of existing molybdenum trioxide, illustrates that catalyst composition activity containing molybdenum center provided by the invention disperses more preferably；By table 3
As a result as can be seen that when catalyst provided by the present invention carries out heavy-oil hydrogenation processing, whole impurity removal activity is than existing skill
Catalyst prepared by art is obviously improved, and is especially promoted more significantly in terms of desulfurization, de- carbon residue and denitrogenation.
Table 1
| Embodiment is numbered | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Bearer number | Z1 | Z2 | Z3 | Z4 |
| Specific surface (rice2/ gram) | 248 | 270 | 254 | 268 |
| Kong Rong (ml/g) | 0.66 | 0.70 | 0.65 | 0.70 |
| It can several bore dias (nm) | 8 | 9 | 8 | 9 |
| Boron (%) | 0.9 | |||
| Silicon (%) | 2.6 | |||
| Fluorine (%) | 4.0 | |||
| Intensity (Newton/millimeter) | 18 | 17 | 18 | 17 |
Table 2
Table 3
Claims (17)
1. a kind of heavy oil hydrogenating treatment catalyst preparation method, this method include：In confined conditions by shaped alumina alumina supporter
Hydro-thermal process is carried out, hydro-thermal process aluminium oxide is obtained；Then by selected from group vib at least one metal component and be selected from VIII group
At least one metal component load on the hydro-thermal process aluminium oxide, obtain heavy oil hydrogenating treatment catalyst；Wherein, with oxygen
Compound meter and on the basis of unit carrier surface load capacity, the content of group vib metal component is 4.8 μm of ol/ in the catalyst
m2-9.0μmol/m2, the content of group VIII metal component is 1.5 μm of ol/m in the catalyst2-4.0μmol/m2；
This method further includes that the hydro-thermal process aluminium oxide before load is dried, without calcination process, the load
The drying temperature of preceding hydro-thermal process aluminium oxide is 60-350 DEG C, and drying time is 1-48 hours.
2. the method according to claim 1, wherein it is counted by oxide and on the basis of unit carrier surface load capacity, it is described to urge
The content of group vib metal component described in agent is 5.4 μm of ol/m2-8.0μmol/m2, the gold of VIII group described in the catalyst
The content for belonging to component is 1.8 μm of ol/m2-3.6μmol/m2。
3. the method according to claim 1, wherein it is counted by oxide and on the basis of unit carrier surface load capacity, it is described to urge
The content of group vib metal component described in agent is 5.9 μm of ol/m2-7.5μmol/m2, the gold of VIII group described in the catalyst
The content for belonging to component is 2.0 μm of ol/m2-3.1μmol/m2。
4. the method according to claim 1, wherein the shaped alumina alumina supporter includes that γ-, η-, θ-, δ-and χ-aluminium oxide are brilliant
At least one of phase crystalline phase.
5. the method according to claim 1, wherein the shaped alumina alumina supporter is with containing selected from boron, fluorine, silicon, titanium, alkaline earth
It is modified processed modified aluminium oxide supports with the compound of at least one of alkali metal modifying element.
6. method according to claim 5, wherein the preparation process of the modified aluminium oxide supports includes：To the forerunner of aluminium oxide
It introduces containing the compound selected from least one of boron, fluorine, silicon, titanium, alkaline earth and alkali metal modifying element in object, then will draw
The aluminum oxide precursor object for having entered the modifying element is molded, and aluminum oxide precursor object after molding is roasted.
7. the method according to claim 1, wherein the shaped alumina alumina supporter is selected from spherical, cylindrical, annular, three leaves
At least one of careless shape, quatrefoil, honeycombed and butterfly shape.
8. the method according to claim 1, wherein the temperature of the hydro-thermal process is 60-180 DEG C, and the time is 1-24 hours, with
Weight meter, the dosage of water is the 100-300 weights % of the formed alumina vehicle weight in the hydro-thermal process.
9. the method according to claim 1, wherein the temperature of the hydro-thermal process is 90-150 DEG C, and the time is 4-12 hours, with
Weight meter, the dosage of water is the 150-250 weights % of the formed alumina vehicle weight in the hydro-thermal process.
10. the method according to claim 1, wherein the group vib metal component is molybdenum and/or tungsten, the group VIII metal group
It is divided into nickel and/or cobalt.
11. the method according to claim 1, wherein the group vib metal component is molybdenum, and the group VIII metal group is divided into nickel
And/or cobalt.
12. the method according to claim 1, wherein by impregnating the group vib metal component and the group VIII metal group
Divide and loads on the hydro-thermal process aluminium oxide.
13. method according to claim 12, wherein this method further includes：Hydro-thermal process aluminium oxide after dipping is done
It is dry, it then carries out roasting or not roasting；The temperature of the drying is 60-150 DEG C, and the dry time is 1-5 hours；The temperature of the roasting
Degree is 350-550 DEG C, and the time of roasting is 1-6 hours.
14. a kind of heavy oil hydrogenating treatment catalyst, which is according to arbitrary in claim 1-13
It is prepared by the method described in one.
15. a kind of heavy oil hydrogenation treatment method, this method include：Under heavy-oil hydrogenation treatment conditions, by heavy oil and claim
Heavy oil hydrogenating treatment catalyst described in 14 contacts and carries out heavy-oil hydrogenation processing.
16. heavy oil hydrogenation treatment method according to claim 15, wherein the heavy oil is selected from crude oil, reduced crude, decompression
At least one of residual oil, deep drawing wax oil, frivolous coal tar and wax tailings.
17. heavy oil hydrogenation treatment method according to claim 15, wherein the heavy-oil hydrogenation treatment conditions include：Reaction temperature
300-550 DEG C of degree, hydrogen partial pressure 4-20 megapascal, liquid hourly space velocity (LHSV) 0.1-3 hours-1, hydrogen to oil volume ratio 200-2500.
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| CN107638882A (en) * | 2017-05-08 | 2018-01-30 | 中国科学院大连化学物理研究所 | A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application |
| CN111821992B (en) * | 2019-04-18 | 2022-08-12 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetallization catalyst |
| CN114471503B (en) * | 2020-10-26 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, catalyst, preparation method and application thereof |
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